Manufacturing derivatives of aldehyde-amine reaction products



Patented Nov. 26, 1929 UNITED STATES PATENT OFFICE WINFIELD SCOTT, OF AKRON, OHIO, ASSIGNOR TO THE RUBBER SERVICE LABORA- TORIES (70., OF AKRON, OHIO, A CORPORATION OF OHIO MANUFACTURING DERIVATIVES F ALDEHYDE-AMINE REACTION PRODUCTS 7 No Drawing. Original application filed September 9, 1925, Serial No. 55,386. a Divided and this application filed May 19,

The present invention is directed to the art of manufacturing certain chemical compounds useful as accelerators of the rubber vulcanization process. The invention is concerned particularly with the process of manufacturing the carbon disulfid derivatives of the reaction product of certain aldehydes and amines as is hereinafter fully set forth and described. The present application is adivision of an application Serial No. 55,386 filed September 9, 1925.

It is well known in chemistry that the aldehydes and particularly the aliphatic aldehydes, react with certain types of organic compounds such as the amines and certain amino derivatives and the like to produce new materials known as condensation products. These products are commonly termed Schifis bases. Not only do aldehydes react in this manner with the primary amino compounds, but they will likewise combine or condense with the secondary amines.

Thus, one molecular proportion of a secondary amino compound, for example, 85 parts of piperidine, may be combined with an aldehyde in its simple or polymeric form, for example with tri-oxy-methylene, in an amount equivalent to molecular proportion of formaldehyde. This quantity will be approximately 15 parts, if paraformaldehyde be used. This reaction may be carried out in the presencepf a suitable solvent or without the use of asofvent, as desired. In either case, a reaction follows at once, and complete combination of the materials with the separation of water of condensation, takes place. The product, in the case of the compounds hereinbefore mentioned, is an oily liquid, having a boiling point of about 237 centigrade and a formula that is substantially as follows:

This compound will react with rbon bisulfid, for example, in an amount equivalent to one molecular proportion thereof, to produce a product which is oily in nature, but which, upon seeding with a crystal or otherwise suitably treating, changes 1nto a crystalline form.

to The carbon bisulfid reaction product of the solved in a solvent'su 1926. Serial No. 110,293.

alkylor beta-alkylpiperidine, the alkyl de-.

rivatives of cyclic amines, tetra-hydro-quinaldine, and di-benzyl-amine and other secondary aliphatic and aromatic amines, the

dialkylamines such as diethylamine as well as hydro-collidine and other compounds present in commercial pyridine may be used. These various compounds and other related materials may be combined in the proportions stated or in other proportions if desired, with aldehydes such as formaldehyde, or acetaldehyde and their polymeric forms, or with propionaldehyde, butraldehyde, isovaleric aldehyde and other aliphatic aldehydes, with acrolein or croto-naldehyde or other unsaturated aldehydes, with oxy-aldehydes such as aldol, or with aromatic aldehydes such as benzaldehyde, cinnamic aldehyde and the like or with ring compounds such as furfuraldehyde, and the product reacted with carbon bisulfid in the manner as described.

It is also apparent from the examples hereinbefore given that other compounds com- 7 prising my referred type of accelerators may be rea ily manufactured. Thus, for example, I may combine di-benzyl-amine, dissolved in any suitable solvent or not, as desired, in the proportion of two molecular proportions thereof with one molecular proportion of paraformaldehyde and obtain a white crystalline product melting at substantially 99 centigrade. This product may be disc as ether and combined with an equal molecular proportion of carbon bisulfid whereupon there is obtained a product which upon recrystallization from 'ligroin, melts at approximately 64 0.

Another t pe of product included within the scope o my presentinvention may be conveniently prepared by reacting two molecular proportions of a di-amine, such as IUD di-ethyl-amine, di-benzyl-amine and analogous compounds with one molecular proportion of paraformaldehyde or a like material. This reaction may be carried out with or without the use of a solvent as desired, but it is necessary that the niixure be kept from becoming 'too hot as the product formed is comparatively low boiling. The product,

which is probably tetra-ethyl-di-amino-methane is a liquid which is slightly soluble in the water separatingout from the reaction mixture. To the product obtained as described, thereis added one molecular proportion of carbon bisulfid. This reaction may be carried out with or without the use of a solvent as desired, but if no solvent be used, the mixture should preferably be maintained "below the boiling point of the product formed.

Another product havingdesirable rubber vulcanization accelerating properties may be prepared by macting two molecular proportlons of piperidine with one molecular found to possess valuable properties as a rubber vulcanization accelerator.

It is to be understood that my invention is not limited by any theory set forth in explanation of the facts involved nor are the examples given to be considered as at all limitative of my invention. My invention is to be regarded as defined solely by the claims hereinafter set forth wherein I intend to claim all novelty permissible in view of the prior art.

\Vhat I claim is: 1. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine IGlCiDlOIl product which comprises reacting a secondary amine with an aldehyde and reacting the product so obtained with carbon disulfid.

2. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine reaction product which comprises reacting two molecular proportions of a secondary amine with one molecular proportion of an aldehyde, and reacting the product so obtained with one molecular proportion of carbon disulfid. Y

3. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine reaction product which comprises reacting two molecular proportions of a di-aryl substituted secondary amine with one molecular proportion of an aliphatic aldehyde, and reacting the product so obtained with one molecular proportion of carbon disulfid.

4. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine reaction product which comprises reacting di-benzyl-amine with a formaldehyde and reacting the product so obtained with carbon disulfid.

5. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine reaction product which comprises reacting two molecular proportions of di-benzylamine with one molecular proportion of a formaldehyde and reacting the product so obtained with one molecular proportion of carbon disulfid.

6. The process of manufacturing the carbon disulfid derivative of an aldehyde-amine reaction product which comprises dissolving two molecular proportions of di-benzylamine in a suitable solvent therefor, adding to the solution one molecular proportion of paraformaldehyde, separating the product, therefrom, dissolving the said product in ether, adding one molecular proportion of carbon disulfid to the solution and removing the solvent by evaporation from the resulting product.

7. The carbon disulfid derivative of an aldehyde-amine reaction product formed by reacting carbon disulfid on the reaction prodnot of a secondary amine with an aldehyde.

8. The carbon disulfid derivative of an aldehyde-amine reaction product formed by reacting one molecular proportion of carbon disulfid on the reaction product of two molecular proportions of a secondary amine with one molecular proportion of an aldehyde.

9. The carbon disulfid derivative of an aldehyde-amine reaction product formed by reacting one molecular proportion of carbon disulfid on the reaction product of one molecular proportion of an aliphatic aldehyde and two molecular proportions of a di-aryl substituted secondary amine.

10. The carbon disulfid derivative of an aldehyde-amine reaction product formed by reacting carbon disulfid with the reaction product of di-benzyl-amine with a formaldehyde.

11. The carbon disulfid derivative of analdehyde-amine reaction product formed by reacting one molecular proportion of carbon disulfid with the reaction product of two molecular proportions' of di-benzyl-amine with one molecular proportion of a'formaldehyde.

Signed at Akron, in the county of Summit and State of Ohio, this 14th day of May, A.

1926. WINFIELD SCOTT. 

